TW201917740A - Method for manufacturing laminate of inorganic substance layer capable of inhibiting the inorganic substance layer from breakage during the manufacturing process - Google Patents

Abstract

Provided is a method for manufacturing a laminate of an inorganic substance layer, which includes: a step of disposing a first supporting film on one side in the thickness direction of a film body having a base film; a step of forming an inorganic substance layer under a vacuum condition on the other side in the thickness direction of the film body; a step of removing the first supporting film; a step of disposing a second supporting film on one side in the thickness direction of the film body; and a step of heating the inorganic substance layer. Furthermore, the first supporting film is provided with a moisture content of less than 2.5 [mu]g/m2.

Description

Method for producing inorganic layered layer body

The present invention relates to a method for producing an inorganic layered laminate, and more particularly to a method for producing an inorganic layered laminate which can be preferably used for optical applications.

Conventionally, a transparent conductive film in which a transparent conductive layer such as indium tin composite oxide (ITO) is formed on a transparent plastic film is used for optical applications such as a film for a touch panel.

For example, Japanese Laid-Open Patent Publication No. 2008-251529 discloses a transparent conductive film having an adhesive layer, which has an amorphous transparent film provided with an amorphous transparent conductive film on one side of a transparent plastic film. The release layer and the release film provided on the other side of the transparent plastic film via the adhesive layer.

In the transparent conductive film with the adhesive layer, an amorphous transparent conductive film is provided on one surface of the transparent plastic film by sputtering under vacuum, and then, on the other side of the transparent plastic film, via an adhesive layer. And configure a specific release film. Further, in the transparent conductive film with the adhesive layer, when the amorphous transparent conductive film is crystallized by the subsequent heat treatment, the occurrence of curl of the transparent conductive film is suppressed by the release film.

However, in recent years, a thin polycycloolefin polymer (COP) substrate can be used as the transparent plastic film for optical characteristics or thinning. The mechanical strength of the thin COP is relatively brittle. Therefore, when an amorphous transparent conductive film is formed by sputtering using a thin COP substrate under vacuum, there is a problem that the thin COP substrate is deformed and broken due to the impact during the transfer or the discharge at the time of sputtering. . As a result, production efficiency is poor.

Therefore, it was investigated that the thin COP substrate was previously reinforced by the above-mentioned release film before forming the amorphous transparent conductive film.

However, in the above documents, a PET (polyethylene terephthalate) film is used as a release film suitable for heat treatment. Since the PET film usually has a large water content, if an amorphous transparent conductive film is formed under vacuum in a state where the thin COP substrate is supported by the PET film, moisture (impurities) evaporate from the surface of the PET film. As a result, the moisture is extracted into the amorphous transparent conductive film (inorganic layer) to deteriorate the characteristics of the amorphous transparent conductive film.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an inorganic layered body which is suppressed from being reduced in the properties of an inorganic layer without breaking.

The present invention [1] includes a method for producing an inorganic layered laminate, comprising: a step of disposing a first support film on a side in a thickness direction of a film body including a base film; and a thickness direction on the other side of the film body a step of forming an inorganic layer under vacuum; a step of removing the first support film; a step of disposing a second support film on a side in the thickness direction of the film; and a step of heating the inorganic layer.

According to this production method, the inorganic layer is formed under vacuum in a state where the film body is placed on the first support film. Therefore, deformation or breakage of the film body can be suppressed at the time of conveyance or formation of the inorganic layer.

Further, after the step of forming the inorganic layer and before the step of heating the inorganic layer, the first supporting film is removed, and the second supporting film is disposed. Therefore, the first support film suitable for forming the inorganic layer and the second support film suitable for heating can be used. Therefore, when the inorganic layer is formed, it is possible to avoid the use of the support film which adversely affects the formation of the inorganic layer under vacuum, and therefore it is possible to suppress the deterioration of the characteristics of the inorganic layer to be formed.

The invention [2] contains the method for producing an inorganic layered product according to [1], wherein the first support film has a water content of less than 2.5 μg/m ² .

According to this production method, since the water content of the first support film is low, when the inorganic layer is formed under vacuum, the moisture evaporated from the first support film can be reduced. Therefore, the moisture which is extracted to the inorganic layer to be formed can be reduced, and the deterioration of the characteristics of the inorganic layer can be suppressed.

The method of producing an inorganic layered product according to the above [1] or [2], wherein the first support film has a fall strength of 10 MPa or less at a width of 10 mm, and an elongation at break of the first support film More than 80%.

According to this manufacturing method, the first support film can be extended with a small tension and the residual stress due to the tension can be reduced. Therefore, when the first support film acts on the supported film body, it is possible to suppress the first support film from imparting residual stress to the film body. As a result, it is possible to suppress the occurrence of curl in the film body.

The method of producing an inorganic layered laminate according to any one of [1] to [3] wherein the first support film is a stretched polypropylene film.

According to this production method, since the first support film has a low water content and a low drop strength and a good elongation, it is possible to suppress the generation of moisture during the formation of the inorganic layer and to suppress the occurrence of curl of the film.

The method for producing an inorganic layered product according to any one of [1] to [4] wherein the peeling force of the first support film and the film body is 0.005 N/50 mm or more and 0.50 N. /50 mm or less.

According to this production method, since the peeling force of the first support film and the film body is 0.005 N/50 mm or more, it is possible to suppress generation of bubbles between the first support film and the like, and to suppress peeling. Further, since the peeling force is 0.50 N/50 mm or less, it is possible to suppress breakage of the base film when the first support film is removed.

The method of producing an inorganic layered product according to any one of [1] to [5] wherein the second support film is a polyethylene terephthalate film.

According to this production method, since the heat shrinkage rate of the second support film is low, the curl of the inorganic layer laminate can be more reliably suppressed.

The method of producing an inorganic layered laminate according to any one of [1] to [6] wherein the substrate film is a cycloolefin polymer film.

According to this production method, the inorganic layered laminate having the cycloolefin polymer film as the base film can be produced without breaking.

The method of producing the inorganic layered layer according to any one of [1] to [7] wherein the step of forming the inorganic layer under vacuum is a step of forming an inorganic layer under vacuum by sputtering. .

According to this manufacturing method, the inorganic material layer (sputter film) having a small thickness can be formed more reliably.

The method of producing an inorganic layered laminate according to any one of [1] to [8] wherein the inorganic layer contains an indium-tin composite oxide.

According to this production method, the transparent conductive film having the inorganic layer having transparent conductivity can be obtained in a state in which transparency and conductivity are good.

According to the method for producing an inorganic layered layered body of the present invention, the inorganic layered layered body in which the deterioration of the characteristics of the inorganic layer is suppressed can be produced without breaking.

In FIG. 1A, the upper and lower sides of the paper are in the vertical direction (thickness direction, first direction), the upper side of the paper is the upper side (the side in the thickness direction, the side in the first direction), and the lower side of the paper is the lower side (the other side in the thickness direction, The first direction is the other side). Further, the left-right direction and the depth direction of the paper surface are the direction orthogonal to the vertical direction. Specifically, the direction arrows are used in accordance with the respective figures. Furthermore, it is not intended to limit the orientation of the inorganic laminate layer of the present invention at the time of manufacture and use by definition of the directions.

<Embodiment> A method for producing the crystallized transparent conductive film 1 which is one embodiment of the method for producing an inorganic layered laminate of the present invention will be described with reference to Figs. 1A to 1G.

The method for producing the crystallized transparent conductive film 1 includes, for example, a first step of preparing a transparent substrate film 2 as an example of a base film; a second step of forming a film body 3; and a third step; The first support film 4 is disposed on the upper side of the film body 3, and the fourth step is formed on the lower side of the film body 3 to form an amorphous transparent conductive layer 5 as an example of the inorganic layer under vacuum; This is to remove the first support film 4; the sixth step is to arrange the second support film 7 on the upper side of the film body 3; and the seventh step of heating the amorphous transparent conductive layer 5. The method for producing the crystallized transparent conductive film 1 is carried out in all of the first to seventh steps by a roll to roll step.

(First Step) In the first step, as shown in FIG. 1A, the transparent base film 2 is prepared.

The transparent base film 2 is a base material for ensuring transparency of the mechanical strength of the crystallized transparent conductive film 1. In other words, the transparent base film 2 supports the crystallized transparent conductive layer 12 together with the hard coat layer (the first hard coat layer 8 and the second hard coat layer 9) and the optical adjustment layer 10 described below.

The transparent base film 2 is a polymer film having a film shape (including a sheet shape) and having transparency. Examples of the material of the transparent base film 2 include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; for example, polymethyl (meth)acrylic resin (acrylic resin and/or methacrylic resin) such as acrylate; for example, polyethylene, polypropylene, cycloolefin polymer (for example, norbornene polymer, cyclopentadiene polymerization) Olefin resin such as a cyclohexadiene polymer; for example, a polycarbonate resin, a polyether oxime resin, a polyarylate resin, a melamine resin, a polyamide resin, a polyimide resin, a cellulose resin, a polyphenylene Vinyl resin, etc. The transparent base film 2 may be used alone or in combination of two or more. The olefin resin is preferably exemplified from the viewpoint of optical properties such as transparency and low birefringence, and a cycloolefin polymer (COP) can be more preferably exemplified.

The total light transmittance (JIS K 7375-2008) of the transparent base film 2 is, for example, 80% or more, preferably 85% or more.

The thickness of the transparent base film 2 is, for example, 200 μm or less, preferably 150 μm or less, preferably 125 μm or less, and further, for example, 10 μm or more, and preferably 25 μm or more. When the thickness of the transparent base film 2 is not more than the above upper limit, the thin film of the crystallized transparent conductive film 1 can be formed. When the thickness of the transparent base film 2 is at least the above lower limit, the crystallized transparent conductive film 1 is excellent in mechanical strength.

In the present invention, the thickness of the film can be measured using a micro-gauge type thickness gauge when the thickness is, for example, 1 μm or more, and can be used, for example, when the thickness is less than 1 μm. The instantaneous multiple metering system performs the measurement.

Further, the transparent base film 2 may be provided with a protective film 15 on the lower surface thereof as shown by the imaginary line in FIG. 1A.

(Second Step) In the second step, as shown in FIG. 1B, the film body 3 is formed.

Specifically, the film body 3 including the first hard coat layer 8, the transparent base film 2, the second hard coat layer 9, and the optical adjustment layer 10 is sequentially formed.

First, the first hard coat layer 8 and the second hard coat layer 9 are provided on the upper surface and the lower surface of the transparent base film 2.

For example, the hard coating composition is wet-coated on each of the upper surface and the lower surface of the transparent substrate film 2, and then dried to form a hard surface on each of the upper surface and the lower surface of the transparent substrate film 2. Coating (first hard coat layer 8 and second hard coat layer 9).

Specifically, for example, a diluent (varnish) obtained by diluting a hard coat composition (described later) with a solvent is prepared, and then the diluent is applied onto the upper surface and the lower surface of the transparent base film 2, and The diluent is dried.

Thereafter, when the hard coat composition contains the active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating the active energy ray after drying the diluted solution.

The hard coat composition contains a resin.

Examples of the resin include a curable resin, a thermoplastic resin (for example, a polyolefin resin), and the like, and a curable resin is preferably used.

Examples of the curable resin include an active energy ray-curable resin which is cured by irradiation with an active energy ray (specifically, ultraviolet rays, electron beams, etc.), for example, a thermosetting resin which is cured by heating, and the like. The active energy ray-curable resin is listed.

The active energy ray-curable resin may, for example, be a polymer containing a functional group having a polymerizable carbon-carbon double bond in its molecule. Examples of such a functional group include a vinyl group, a (meth) acrylonitrile group (methacryl fluorenyl group and/or an acryl fluorenyl group).

Specific examples of the active energy ray-curable resin include (meth)acrylic ultraviolet curable resins such as urethane acrylate and epoxy acrylate.

In addition, examples of the curable resin other than the active energy ray-curable resin include a urethane resin, a melamine resin, an alkyd resin, a siloxane polymer, and an organic decane condensate.

These resins may be used alone or in combination of two or more.

The hard coat composition may further contain particles. Thereby, the hard coat layer can be set as an anti-blocking layer having blocking resistance.

Examples of the particles include inorganic particles, organic particles, and the like. Examples of the inorganic particles include cerium oxide particles; metal oxide particles containing, for example, zirconia, titanium oxide, zinc oxide, and tin oxide; and carbonate particles such as calcium carbonate. Examples of the organic particles include crosslinked acrylic resin particles and the like. The particles may be used singly or in combination of two or more.

The hard coating composition may further contain a known additive such as a leveling agent, a thixotropic agent, or an antistatic agent.

Then, on the lower surface of the second hard coat layer 9, an optical adjustment layer 10 is provided.

For example, the optical adjustment layer 10 is formed on the lower surface of the second hard coat layer 9 by wet coating the optical adjustment composition on the lower surface of the second hard coat layer 9 and then drying.

Specifically, for example, a diluent obtained by diluting the optically adjusting composition with a solvent is prepared as needed, and then the diluted solution is applied onto the lower surface of the second hard coat layer 9, and the diluted solution is dried.

When the optical adjustment composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating the active energy ray after drying the diluent.

The optical conditioning composition contains a resin, preferably containing a resin and particles.

The resin is not particularly limited, and examples thereof are the same as those used in the hard coat composition. The resin may be used singly or in combination of two or more. A curable resin is preferably exemplified, and an active energy ray-curable resin can be more preferably exemplified.

The content ratio of the resin is, for example, 10% by mass or more, preferably 25% by mass or more, and for example, 95% by mass or less, preferably 60% by mass or less, based on the optically-adjusting composition.

As the particles, a preferable material can be selected depending on the refractive index required for the optical adjustment layer, and for example, the same as those used in the hard coat composition can be mentioned. The particles may be used singly or in combination of two or more. The inorganic particles are preferably exemplified, and metal oxide particles are more preferably exemplified, and zirconia particles (ZnO ₂ ) are further preferably exemplified.

The content ratio of the particles is, for example, 5% by mass or more, preferably 40% by mass or more, and for example, 90% by mass or less, preferably 75% by mass or less, based on the optically-adjusting composition.

The optical adjustment composition may further contain a known additive such as a leveling agent, a thixotropic agent, or an antistatic agent.

Thereby, the optical adjustment layer 10, the second hard coat layer 9 disposed on the optical adjustment layer 10, the transparent base film 2 disposed on the second hard coat layer 9, and the transparent base film are obtained. The film body 3 (film laminate) of the first hard coat layer 8 on the top of 2.

The first hard coat layer 8 and the second hard coat layer 9 are used to crystallize the surface of the transparent conductive film 1 (the crystallized transparent conductive layer 12) when a plurality of crystallized transparent conductive films 1 are laminated. Surface) A scratch protective layer that is less prone to scratching. Moreover, it is also possible to provide an anti-blocking layer for imparting blocking resistance to the crystallized transparent conductive film 1.

For example, the thickness of each hard coat layer is, for example, 0.5 μm or more, preferably 1 μm or more, and is, for example, 10 μm or less, preferably 3 μm or less.

The optical adjustment layer 10 is a layer that adjusts the crystallized transparent conductive film 1 to ensure excellent transparency while suppressing the visibility of the wiring pattern in the crystallized transparent conductive layer 12. Optical properties (for example, refractive index) of the film 1.

The refractive index of the optical adjustment layer 10 is, for example, 1.6 or more, preferably 1.8 or less.

The thickness of the optical adjustment layer 10 is, for example, 50 nm or more, preferably 80 nm or more, and is, for example, 300 nm or less, preferably 150 nm or less.

The thickness of the film body 3 is, for example, 15 μm or more, preferably 25 μm or more, and is, for example, 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

When the transparent base film 2 is provided with the protective film 15 on the lower surface thereof, the protective film 15 is removed by peeling, melting, or the like before the formation of the second hard coat layer 9.

(Third Step) In the third step, as shown in FIG. 1C, the first support film 4 is disposed on the upper side of the film body 3.

Specifically, the first support film 4 is placed on the upper surface of the film body 3 so that the upper surface of the first hard coat layer 8 is in contact with the lower surface of the first support film 4. Thereby, the film body 3 is bonded to the first support film 4.

The arrangement of the first support film 4 is preferably carried out under the atmosphere.

The first support film 4 supports the transparent base film 2 in the fourth step of forming the amorphous transparent conductive layer 5 under vacuum.

The lower surface of the first support film 4 is preferably viscous (adhesive). Thereby, the first support film 4 and the film body 3 can be directly bonded together.

The fall strength of the first support film 4 is, for example, lower than the fall strength of the second support film 7 (described later). Specifically, when the width is 10 mm, it is, for example, 30 MPa or less, preferably 10 MPa or less. Further, the elongation at break of the first support film 4 is, for example, greater than the elongation at break of the second support film, and specifically, for example, 80% or more, preferably 100% or more.

When the fall strength of the first support film 4 is equal to or less than the above-described upper limit, and the elongation at break of the first support film 4 is at least the above lower limit, the first support film 4 can be extended with a small tension and can be lowered. Residual stress due to tension. Therefore, even in the case where the first support film laminate 21 (described later) strongly acts on the tension in the transport direction in the roll-to-roll step, the residual stress remaining in the first support film 4 can be reduced. Therefore, the residual stress applied to the film body 3 by the first support film 4 can be lowered. As a result, the occurrence of curl can be suppressed in the film body 3.

The undulation stress and the rupture elongation can be measured by cutting the measurement target film (for example, the first support film 4) to a width of 10 mm × a length of 10 mm, and setting it on a measuring device (Shimadzu Corporation) It is manufactured by the company under the trade name "Autograph AG-I 10KN" and stretched at a stretching speed of 5 mm/s to 100 mm/s.

The water content of the first support film 4 is, for example, lower than the water content of the second support film 7 (described later), for example, less than 2.5 μg/m ² , preferably 1.0 μg/m ² or less. When the water content of the first support film 4 is not more than the above upper limit, when the amorphous transparent conductive layer 5 is formed under vacuum, the moisture evaporated from the lower surface (exposed surface) of the first support film 4 can be surely reduced. Therefore, the moisture (impurities) drawn to the amorphous transparent conductive layer 5 to be formed can be reduced, and the characteristics of the amorphous transparent conductive layer 5 (and, further, the crystallized transparent conductive layer 12) can be suppressed (for example, conductivity, Reduced transparency).

The water content can be determined by Karl Fischer moisture measurement. Specifically, it can be measured using a Karl Fischer measuring device that introduces a gas generated by a heating vaporization method (150 ° C) into a titration tank.

The linear thermal expansion coefficient of the first support film 4 is, for example, more than 2.0 × 10 ^-5 / ° C, preferably 1.5 × 10 ^-4 / ° C or more, and further, for example, 1.0 × 10 ^-2 / ° C or less.

The material of the first support film 4 is, for example, an olefin resin, and more preferably an extended polypropylene (OPP). The OPP film has a low water content, a low drop strength, and a good elongation. Therefore, at the time of formation of the amorphous transparent conductive layer 5, generation of moisture (impurities) can be more reliably suppressed. At the same time, since the residual stress due to the tension of the roll-to-roll step is low, the occurrence of curl of the film 3 can be suppressed. Further, since the OPP film has adhesiveness, the first support film 4 can be directly placed (bonded) on the upper surface of the film body 3 without passing through the adhesive layer, and the film body 3 can be peeled off from the first support film 4. The force has become good.

Thereby, the first support film laminate 21 including the film body 3 and the first support film 4 disposed on the film body 3 is obtained.

In the first support film laminate 21, the peeling force of the film body 3 and the first support film 4 is, for example, 0.50 N/50 mm or less, preferably 0.20 N/50 mm or less, and further, for example, 0.005 N/50. Above mm, preferably 0.15 N/50 mm or more. When the peeling force is equal to or less than the above-described upper limit, the first support film 4 can be easily peeled off from the amorphous transparent conductive film 6 in the removal step of the first support film 4 described below, and the transparent base film 2 can be suppressed. fracture. In addition, when the peeling force is equal to or higher than the lower limit, it is possible to suppress the generation and increase of bubbles between the film body 3 and the first support film 4 during the arrangement of the first support film 4 or the formation of the amorphous transparent conductive layer 5. It is large enough to prevent it from peeling off and falling off.

The peeling force can be obtained by cutting the first support film laminate 21 into a width of 50 mm × a length of 50 mm, and using a universal tensile tester at a peeling speed of 300 mm/min and peeling off. The measurement was carried out at an angle of 180 °.

The thickness of the first support film 4 is, for example, 15 μm or more, preferably 30 μm or more, and is, for example, 150 μm or less, preferably 100 μm or less.

(Step 4) In the fourth step, as shown in Fig. 1D, an amorphous transparent conductive layer 5 is formed on the lower side of the film body 3 under vacuum.

Specifically, an amorphous transparent conductive layer 5 is formed on the lower surface of the optical adjustment layer 10 by a dry method under vacuum.

The vacuum condition (air pressure) is, for example, 100 Pa or less, preferably 10 Pa or less, more preferably 1 Pa or less.

Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. A sputtering method can be preferably exemplified. By this method, the amorphous transparent conductive layer 5 (sputtering film) having a small thickness can be formed more surely.

In the case of the sputtering method, the following inorganic substance constituting the amorphous transparent conductive layer 5 is exemplified as the target, and ITO is preferably used. The tin oxide concentration of ITO is, for example, 0.5% by mass or more, preferably 3% by mass or more, and for example, 15% by mass or less, preferably 13 or more, from the viewpoint of durability and crystallization of the ITO layer. Below mass%.

Examples of the sputtering gas include an inert gas such as Ar. Further, a reactive gas such as oxygen can be used in combination as needed. When the reactive gas is used in combination, the flow rate ratio of the reactive gas is not particularly limited, and is, for example, 0.1% by flow or more and 5% by flow or less based on the total flow rate ratio of the sputtering gas and the reactive gas.

The power source used in the sputtering method may be, for example, a DC (direct current) power source, an AC (alternating current) power source, an MF (medium frequency) power source, and an RF (radio frequency) power source. One, in addition, can also be a combination of them.

Thereby, an amorphous (amorphous) transparent conductive layer 5 is formed on the lower surface of the film body 3. As a result, the amorphous transparent conductive film 6 including the amorphous transparent conductive layer 5 and the film body 3 disposed on the amorphous transparent conductive layer 5 is obtained while being supported by the first support film 4. In other words, the second support film laminate 22 including the amorphous transparent conductive film 6 and the first support film 4 disposed on the amorphous transparent conductive film 6 is obtained.

The material of the amorphous transparent conductive layer 5 includes, for example, a group selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. At least one metal oxide of a metal. In the metal oxide, a metal atom shown in the above group may be further doped as needed.

Specific examples of the amorphous transparent conductive layer 5 include an oxide containing indium such as indium tin composite oxide (ITO), and an oxide containing antimony such as antimony-tin composite oxide (ATO). From the viewpoint of good transparency and conductivity, an oxide containing indium is preferable, and ITO is more preferably used.

The "ITO" in the present specification may be a composite oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these. Examples of the additional component include metal elements other than In and Sn, and specific examples thereof include Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, and Fe. Pb, Ni, Nb, Cr, Ga, and the like.

The thickness of the amorphous transparent conductive layer 5 is, for example, 10 nm or more, preferably 20 nm or more, and further, for example, 50 nm or less, preferably 30 nm or less.

(Fifth Step) In the fifth step, as shown in FIG. 1E, the first support film 4 is removed. That is, the first support film 4 is removed from the second support film laminate 22 .

Specifically, in the second support film laminate 22, the first support film 4 is peeled off from the upper surface of the amorphous transparent conductive film 6.

Thereby, the amorphous transparent conductive film 6 including the amorphous transparent conductive layer 5 and the film body 3 disposed on the amorphous transparent conductive layer 5 is obtained.

(Sixth Step) In the sixth step, as shown in FIG. 1F, the second support film 7 is disposed on the upper side of the amorphous transparent conductive film 6.

Specifically, the second support film 7 is placed on the upper surface of the amorphous transparent conductive film 6 (that is, the upper surface of the first hard coat layer 8) via the adhesive layer 11. Thereby, the amorphous transparent conductive film 6 is bonded to the second support film 7 via the adhesive layer 11.

The arrangement of the second support film 7 is preferably carried out under the atmosphere.

Examples of the adhesive constituting the adhesive layer 11 include an acrylic adhesive, a rubber adhesive (such as a butyl rubber adhesive), a polyoxygen adhesive, a polyester adhesive, and a polyamine adhesive. An acid ester type adhesive, a polyamidamide type adhesive, an epoxy type adhesive, a vinyl alkyl ether type adhesive, a fluororesin type adhesive, etc.

Examples of the application method of the adhesive include a doctor blade, a gravure coater, a spray coater, a coater, a spin coater, and a roll coater.

The thickness of the adhesive layer 11 is, for example, 1 μm or more, preferably 5 μm or more, and is, for example, 300 μm or less, preferably 50 μm or less.

The second support film 7 supports the amorphous transparent conductive film 6 in the heating step. In addition, when the crystallized transparent conductive film 1 obtained is protected, transported, and stored, it is bonded (disposed) to the crystallized transparent conductive film 1 before use of the crystallized transparent conductive film 1. In other words, even when the product is shipped as a product, the second support film 7 is bonded to the crystallized transparent conductive film 1 as a protective film.

The fall strength of the second support film 7 is, for example, more than 30 MPa, preferably 50 MPa or more, when the width is 50 mm. The elongation at break of the second support film 7 is, for example, less than 80%. When the lodging strength of the second support film 7 is not less than the above lower limit or the elongation at break is less than the above upper limit, when the tension is applied to the amorphous transparent conductive film 6 and the second support film 7, the film can be suppressed. Warping.

The water content of the second support film 7 is, for example, 2.5 μg/m ² or more, preferably 5.0 μg/m ² or more, and is, for example, 10 μg/m ² or less.

The linear thermal expansion coefficient of the second support film 7 is, for example, lower than the thermal linear expansion coefficient of the first support film 4, and specifically, for example, 2.0 × 10 ^-5 / ° C or less, preferably 1.0 × 10 ^-5 / ° C or less. When the thermal expansion coefficient of the second support film 7 is equal to or less than the above upper limit, heat shrinkage of the second support film 7 can be reduced in the heating step, and generation of curl of the crystallized transparent conductive film 1 can be suppressed.

The second support film 7 is a film different from the first support film 4, and examples of the material thereof include an olefin resin and a polyester resin, and COP and PET are preferable, and PET is more preferably used. Since the heat shrinkage of the COP film or the PET film is low, the occurrence of curl of the crystallized transparent conductive film 1 can be further suppressed.

The thickness of the second support film 7 is, for example, 50 μm or more, preferably 100 μm or more, and is, for example, 300 μm or less, or preferably 200 μm or less.

As a method of disposing the second support film 7 on the amorphous transparent conductive film 6 via the adhesive layer 11, for example, an adhesive can be applied to the upper surface of the amorphous transparent conductive film 6, and then the first support is provided. The film 4 is disposed on the upper surface of the adhesive layer 11, and, for example, the second support film 7 on which the adhesive layer 11 is disposed on the lower surface, and the amorphous transparent conductive film 6 is brought into contact with the adhesive layer 11 .

Thereby, the third support film including the amorphous transparent conductive film 6, the adhesive layer 11 disposed on the amorphous transparent conductive film 6, and the second support film disposed on the adhesive layer 11 is obtained. Laminated body 23.

(Step 7) In the seventh step, as shown in Fig. 1G, the amorphous transparent conductive layer 5 is heated.

Specifically, the third support film laminate 23 is subjected to heat treatment.

The heat treatment is preferably carried out under the atmosphere. The heat treatment can be carried out, for example, using an infrared heater, an oven, or the like.

The heating temperature is, for example, 100 ° C or higher, preferably 120 ° C or higher, and further, for example, 200 ° C or lower, preferably 160 ° C or lower. When the heating temperature is within the above range, the crystal transformation can be surely performed while suppressing thermal damage of the transparent base film 2 and impurities generated from the transparent base film 2.

The heating time can be appropriately determined depending on the heating temperature, and is, for example, 10 minutes or longer, preferably 30 minutes or longer, and further, for example, 5 hours or shorter, preferably 3 hours or shorter.

Thereby, the amorphous transparent conductive layer 5 is crystallized to form the crystallized transparent conductive layer 12. As a result, as shown in FIG. 1G, the crystallized transparent conductive layer 12 and the film body disposed on the crystallized transparent conductive layer 12 are obtained while being supported by the second support film 7 via the adhesive layer 11. The crystallized transparent conductive film 1 of 3. In other words, the transparent conductive film having the crystallized transparent conductive film 1 and the adhesive layer 11 disposed on the crystallized transparent conductive film 1 and the second support film disposed on the adhesive layer 11 is obtained. Sex film 24.

The transparent conductive film 24 with a support film is used to remove (peel) the adhesive layer 11 and the second support film 7 at the time of use, and the crystallized transparent conductive film 1 is used as a monomer.

(Crystalized Transparent Conductive Film) The crystallized transparent conductive film 1 is, for example, a component such as a base material for a touch panel provided in an image display device, that is, an image display device. In other words, the crystallized transparent conductive film 1 is used to form a component such as an image display device, and does not include an image display element such as an LCD (liquid crystal display) module, but the parts are separately distributed and industrially. A device that can be used. Specifically, the crystallized transparent conductive film 1 is provided with the first hard coat layer 8 , the transparent base film 2 , the second hard coat layer 9 , the optical adjustment layer 10 , and the crystallized transparent conductive layer 12 in this order.

When the crystallized transparent conductive film 1 is used as a substrate for a touch panel, for example, various forms such as an optical method, an ultrasonic method, a capacitance method, and a resistive film method can be used as the touch panel. It is especially useful for capacitive touch panels.

According to the method for producing the crystallized transparent conductive film 1, the amorphous transparent conductive layer 5 is formed under vacuum in a state where the film body 3 is placed (supported) on the first support film 4. Therefore, deformation or breakage of the film body 3 can be suppressed at the time of conveyance or formation of the amorphous transparent conductive layer.

Further, after the step of forming the amorphous transparent conductive layer 5 and before the step of heating the amorphous transparent conductive layer 5, the first support film 4 is removed and the second support film 7 is placed. Therefore, the first support film 4 suitable for forming the amorphous transparent conductive layer 5 and the second support film 7 suitable for heating can be used. Therefore, when the amorphous transparent conductive layer 5 is formed, it is possible to avoid the use of a support film (specifically, a film having a large water content) which adversely affects the formation of the amorphous transparent conductive layer 5 under vacuum, and adopts appropriate Since the first support film 4 is provided, it is possible to suppress a decrease in characteristics (transparency and conductivity) of the amorphous transparent conductive layer 5 to be formed. Further, when the amorphous transparent conductive layer 5 is heated, the support film having a large heat shrinkage can be avoided, and the second support film 7 having a low heat shrinkage can be used. Therefore, the crystallized transparent conductive film 1 to be obtained can be suppressed. curly.

Further, in the production method, particularly in the case where the transparent base film 2 is a film having a relatively strong mechanical strength (for example, a thin cycloolefin polymer film), it is possible to preferably manufacture the transparent substrate without breaking. The transparent conductive film 1 of the film 2 is crystallized.

(Variation) A modification of an embodiment of the method for producing the crystallized transparent conductive film 1 of the present invention will be described with reference to Figs. 2A-F. In the modified example, the same members as those in the embodiment are denoted by the same reference numerals, and their description will be omitted.

(1) In the embodiment shown in FIGS. 1A-G, the film body 3 includes the first hard coat layer 8, the second hard coat layer 9, and the optical adjustment layer 10. However, for example, as shown in FIGS. 2A-F, Generally, the film body 3 does not have part or all of the layers. For example, in the embodiment shown in Figs. 2A-F, the film body 3 is merely an example of the transparent substrate film 2. In the embodiment shown in FIGS. 2A-F, as shown in FIG. 2B, in the third step, the first support film 4 is directly disposed on the upper surface of the transparent substrate film 2, as shown in FIG. 2C. In the step, the amorphous transparent conductive layer 5 is directly formed on the lower surface of the transparent substrate film 2. As shown in FIG. 2D, in the fifth step, the first support film 4 is removed from the transparent substrate film 2, as shown in FIG. 2E. In the sixth step, the second support film 7 is placed directly on the upper surface of the transparent base film 2 via the adhesive layer 11.

(2) In the embodiment shown in FIGS. 1A to 1G, a pattern such as a wiring pattern is not formed on the crystallized transparent conductive layer 12. However, for example, although not shown, a pattern can be formed on the crystallized transparent conductive layer 12. Specifically, the amorphous transparent conductive layer 5 or the crystallized transparent conductive layer 12 is etched by a known etching method before or after the heating step, whereby the transparent conductive layer 12 can be patterned.

(3) In the embodiment shown in FIGS. 1A-G, the first to seventh steps are performed while conveying the transparent base film 2 in a roll-to-roll manner. However, for example, although not shown, a batch may be used. The method (single-chip method) forms part or all of the first to seventh steps. From the viewpoint of productivity, it is preferred to carry out the first to seventh steps in a roll-to-roll manner. Further, in the roll-to-roll step, the first to seventh steps may be continuously performed, and the first to seventh steps may be intermittently performed.

(4) In the embodiment shown in FIGS. 1A to 10G, in the third step, the first support film 4 is directly disposed on the upper surface of the film body 3. However, for example, although not shown, the film may be formed on the film body. The first support film 4 is placed on the upper surface of the third layer via the adhesive layer.

The adhesive layer may be the same as the adhesive layer 11 described above in the sixth step.

<Another embodiment> In the embodiment shown in FIG. 1A to FIG. 1G, the method for producing the crystallized transparent conductive film 1 is exemplified as one embodiment of the method for producing the inorganic layered laminate. herein. For example, although not shown, a method for producing a gas barrier film is exemplified as another embodiment of a method for producing an inorganic layered laminate. The gas barrier film is provided with a gas barrier layer containing a gas barrier inorganic material, and a base film. As such a gas barrier layer and a base film, a known one can be used, and for example, those disclosed in JP-A-2011-149057 can be cited.

Furthermore, the invention described above is provided as an exemplified embodiment of the invention, but is merely illustrative and should not be construed as limiting. Variations of the invention as clarified by those skilled in the art are included in the scope of the following claims.

1‧‧‧Crystalized transparent conductive film

2‧‧‧Transparent substrate film

3‧‧‧membrane body

4‧‧‧1st support film

5‧‧‧Amorphous transparent conductive layer

6‧‧‧Amorphous transparent conductive film

7‧‧‧2nd support film

8‧‧‧1st hard coat

9‧‧‧2nd hard coat

10‧‧‧Optical adjustment layer

11‧‧‧Adhesive layer

12‧‧‧ Crystallized transparent conductive layer

15‧‧‧Protective film

21‧‧‧1st Supporting Membrane

22‧‧‧2nd support film laminate

23‧‧‧3rd Supporting Membrane

24‧‧‧Transparent conductive film with support film

1A-G are process diagrams showing an embodiment of a method for producing an inorganic layered product of the present invention, wherein Fig. 1A shows a first step of preparing a transparent substrate film, and Fig. 1B shows a second step of forming a film body, and Fig. 1C shows The third step of arranging the first support film, FIG. 1D shows the fourth step of forming the amorphous transparent conductive layer, FIG. 1E shows the fifth step of removing the first support film, and FIG. 1F shows the sixth step of arranging the second support film. Figure 1G shows the seventh step of heating the amorphous transparent conductive layer. 2A-F are process diagrams showing a modification of an embodiment of a method for producing an inorganic layered product according to the present invention, wherein Fig. 2A shows a first step of preparing a transparent substrate film, and Fig. 2B shows a third step of arranging a first support film. Step 2C shows a fourth step of forming an amorphous transparent conductive layer, FIG. 2D shows a fifth step of removing the first supporting film; FIG. 2E shows a sixth step of arranging the second supporting film, and FIG. 2F shows heating of amorphous transparent conductive Step 7 of the layer.

Claims (9)

A method for producing an inorganic layered product, comprising: a step of disposing a first supporting film on a side in a thickness direction of a film body including a base film; and forming an inorganic substance under vacuum in the other side in the thickness direction of the film body a step of removing the first support film; a step of disposing the second support film on the side in the thickness direction of the film; and a step of heating the inorganic layer. The method for producing an inorganic layer laminate according to claim 1, wherein the first support film has a water content of less than 2.5 μg/m ² . The method for producing an inorganic layer laminate according to claim 1, wherein the first support film has a fall strength of 30 MPa or less when the width is 10 mm, and the elongation at break of the first support film is 80% or more. The method for producing an inorganic layer laminate according to claim 1, wherein the first support film is a stretched polypropylene film. The method for producing an inorganic layer laminate according to claim 1, wherein the peeling force of the first support film and the film body is 0.005 N/50 mm or more and 0.50 N/50 mm or less. The method for producing an inorganic layer laminate according to claim 1, wherein the second support film is a polyethylene terephthalate film. The method for producing an inorganic layer laminate according to claim 1, wherein the substrate film is a cycloolefin polymer film. The method for producing an inorganic layered body according to claim 1, wherein the step of forming the inorganic layer under vacuum is a step of forming an inorganic layer under vacuum by a sputtering method. The method for producing an inorganic layered product according to claim 1, wherein the inorganic layer contains an indium-tin composite oxide.